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 - A novel polymorph of 3-[(2-{[4-(hexyloxycarbonylamino-
imino-methyl)-phenylamino]- methyl}-l-methyl-lH-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester (dabigatran etexilate)
2. Applicant(s)
(a) NAME: ALEMBIC PHARMACEUTICALS LIMITED
(b) NATIONALITY: An Indian Company.
(c) ADDRESS: Alembic Campus, Alembic Road,
Vadodara-390, 003, Gujarat, India
3. PREAMBLE TO THE DESCRIPTION
The following specification particularly describes the invention and the manner in which is to be
performed:

FIELD OF THE INVENTION
A novel polymorph of 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]-methyl}-1-methyl-1H-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate)

BACKGROUND OF THE INVENTION
The invention relates to new polymorphs of the active substance Dabigatran etexilate, processes for the preparation thereof and the use thereof as pharmaceutical compositions. This active substance with the chemical formula I

is already known from WOl99837075, wherein compounds with a thrombin-inhibiting
and thrombin time-prolonging activity are disclosed, under the name 3-[(2-{[4-
(hexyloxycarbonylamino-imino-methyl)-phenylamino]- methyl} -1 -methyl-1H-
benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate). The compound of formula I is a double prodrug of the compound


i.e. the compound of formula I is only converted into the actual effective compound, namely the compound of formula II, in the body. The main fields of application of the compound of chemical formula I are the post-operative prophylaxis of deep vein thrombosis and the prevention of stroke.
Dabigatran etexilate was first described in WOl99837075 by Hauel et al. According to Example 113 of said patent specification dabigatran etexilate of the formula II is prepared in an analogous manner to the process described in Example 90 by reacting l-methyl-2-[N-(4-amidino-pheny])-aminomethyl]-5-benzirnidazol-carbonate-N-(2-pyridyl)-A)-[2-(ethoxy- carbonyl)-ethyl]-amid hydrochloride and hexyl chloroformate. The thus-formed base is characterized by thin layer chomatography and mass spectrometry. No information is provided in the description relating to the crystallographic properties of the dabigatran etexilate base.
The same process described in the aboye patent is disclosed in a publication of Hauel et al. (J Med. Chem. 2002, 45, 1757-1766), wherein the dabigatran etexilate base is characterized by melting point (128- 129°C) and [Eta]-NMR.
Three polymorphic forms of dabigatran etexilate mesylate are described in WO2005028468. The polymorphic forms obtained from the base by crystallization (Form I, II and hemihydrate) are characterized by X-ray powder diffraction pattern and differential scanning calorimetry curves.
In WO20061144156 salts of dabigatran etexilate are described, such as the hydrochloride, citrate, tartarate, malonate, maleate and salicilate salts. These salts are not characterized by powder X-ray diffraction patterns, only by differential scanning calorimetry curves. The melting points ranked in order are as follows: 135°C, 170°C, 160°C, 100°C, 120°C, and 155 °C.
In WO20061314913 polymorphic forms of the dabigatran etexilate base are described. The polymorphic forms obtained by crystallization are characterized by X-ray powder

diffraction patterns, differential scanning calorimetry curves and thermogravimetric measurements data.
In WO 2008043759 further dabigatran etexilate salts and polymorphic forms thereof are described, such as two polymorph (I and II) of the salt formed with phosphoric acid, two polymorph (III and IV) of the salt formed with fumaric acid, three polymorph (I, II and V) of the salt formed with oxalic acid, three polymorph (II, V and VI) of the salt formed with hydrogen chloride and four polymorph (I, V, VI and VII) of the salt formed with p-toluenesulfonic acid. The polymorphic forms are characterized by X-ray powder diffraction pattern. Furthermore, Form IV of the salt formed with fumaric acid and four Forms (I, V, VI and VII) of the salt formed with p-toluenesulfonic acid are characterized by differential scanning calorimetry curves, too.
In WO2008059029 two further anhydrous forms and three solvates of the dabigatran etexilate base are described. The anhydrous forms III and IV, the rnonohydrate forms I and II and the nitrobenzene solvate form I are characterized by X-ray powder diffraction pattern and differential scanning calorimetry curves.
The aim of the invention is to provide new polymorphs of the compound of formula I having advantageous properties for pharmaceutical use.
The above-mentioned pharmacologically beneficial properties of the disubstituted bicyclic heterocycles disclosed in the prior art are the main prerequisite for effective use of the compounds as pharmaceutical compositions. An active substance must, however, also meet other requirements in order to be capable of being used as a pharmaceutical composition. These parameters are to a large extent connected with the physicochemical nature of the active substance.
Without being restricted thereto, examples of these parameters are the stability of effect of the starting substance under different ambient conditions, stability in the course of the preparation of the pharmaceutical formulation and stability in the final compositions of

the pharmaceutical preparation. The pharmaceutical active substance used to prepare the pharmaceutical compositions should therefore have high stability, which should also be guaranteed even under different environmental conditions. This is absolutely essential to prevent the use of pharmaceutical compositions which contain, in addition to the active substance itself, breakdown products thereof, for example. In such cases the content of active substance found in the pharmaceutical formulations might be less than specified. The absorption of moisture reduces the content of pharmaceutically active substance as a result of the increased weight caused by the uptake of water. Pharmaceutical compositions with a tendency to absorb moisture have to be protected from moisture during storage, e.g. by the addition of suitable drying agents or by storing the drug in an environment where it is protected from moisture. In addition, the uptake of moisture may reduce the content of pharmaceutically active substance during manufacture if the pharmaceutical substance is exposed to the environment without being protected from moisture in any way. Preferably, therefore, a pharmaceutically active substance should be only slightly hygroscopic.
As the crystal modification of an active substance is important to the reproducible active substance content of a preparation, there is a need to clarify as far as possible any existing polymorphism of an active substance present in crystalline form. If there are different polymorphic modifications of an active substance, care must be taken to ensure that the crystalline modification of the substance does not change in the pharmaceutical preparation later produced from it. Otherwise, this could have a harmful effect on the reproducible potency of the drug.
Another criterion which may be of exceptional importance under certain circumstances depending on the choice of formulation or the choice of manufacturing process is the solubility of the active substance. If for example pharmaceutical solutions are prepared (e.g. for infusions), it is essential that the active substance should be sufficiently soluble in physiologically acceptable solvents. It is also very important for drugs which are to be taken orally that the active substance should be sufficiently soluble.

The problem of the present invention is to provide a pharmaceutically active substance which not only is characterised by high pharmacological potency but also satisfies the above-mentioned physicochemical requirements as far as possible.
OBJECT OF THE INVENTION
The object of the present invention to provide novel polymorph of 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino] -methyl}-1 -methyl-1H-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate) referred to as form A.
Another object of the present invention to provide process for the preparation of novel polymorph of 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]-methyl}-1 -methyl-lH-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate) referred to as form A
SUMMARY OF THE INVENTION
In one aspect, the present invention to provide novel polymorph of 3-[(2-{[4-
(hexyloxycarbonylamino-imino-methyl)-phenylamino]- methyl} -1 -methyl-1H-
benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate) referred to as form A.
In a another aspect the present invention relates to the above-mentioned polymorphic form of the active substance 3-[(2-{[4-(hexyloxycarbonylammo-imino-methyl)-phenylamino]- methyl}-1-methyl-lH-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester, in crystalline form, referred to as form A characterised by XRD.
In a another aspect the present invention relates to the above-mentioned polymorphic form of the active substance 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-

phenylamino]- methyl}-1 -methyl-1H-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester, in crystalline form, referred to as form A characterised by melting points of T mp. =133±5°C (determined by DSC; evaluation by peak maximum; heating rate: 10°C./min).
In a another aspect the present invention relates to the above-mentioned polymorphic form of the active substance 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino] - methyl}-1 -methyl-1H-benzimidazole-5 -carbonyl)-pyridin-2-yl -amino] -propionic acid ethyl ester, in crystalline form, referred to as form A characterised by TGA.
In a another aspect the present invention relates to the above-mentioned polymorphic form of the active substance 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]- methyl} -1 -methyl-1 H-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester, in crystalline form, referred to as form A characterised by XRD, DSC, TGA Fig.
BRIEF DESCRIPTION OF THE DRAWING
Fig. 1 shows the X-ray powder diffraction pattern of new polymorph Form A of 3-[(2-
{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]- methyl} -1 -methyl-1H-
benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate).
Fig. 2 shows the DSC of new polymorph Form A of 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]- methyl}-l-methyl-lH-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate) .
Fig. 3 shows the TGA of new polymorph Form A of 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]- methyl}-1 -methyl-1 H-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate).

DETAILED DESCRIPTION OF THE INVENTION
Surprisingly it has now been found that the novel polymorphs of new polymorph Form A of 3-[(2- {[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]- methyl} -1 -methyl-lH-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate) meet these requirements and have advantageous properties.
Here the term "crystallizing" means crystallizing compounds using methods known in the art. For example either reducing the volume of the solvent with respect to solute or decreasing the temperature of the solution or using both so as to crystallize the compound.
The term "treating" as used hereinabove refers to suspending, dissolving or mixing and contacting or reacting of product with solvent or reagents followed by isolating product by removal of reagents and solvents.
The term "triturating" as used hereinabove refers to suspending product in solvent and stirring for period of time sufficient for surface contact of solid with solvent and then filtering the compound from the mixture.
The first embodiment, of the present invention relates to the novel polymorph of new polymorph Form A of 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]-methyl}-l-methyl-lH-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate).
In another embodiment, the present invention, relates to a novel polymorph Form A of 3-[(2 - {[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]- methyl} -1 -methyl-1H-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate) characterized by an X-ray powder diffraction (XRD) pattern having peaks expressed at 2θ at about 4.9, 8.8, 9.2, 9.7, 10.4, 12.7, 13.3, 13.8,

14.7, 15.5, 18.0, 18.9, 20.1, 20.8, 21.6, 22.3, 22.7, 23.3, 23.8, 24.2, 24.7, 26.8, 27.4, 28.2, 28.7, 29.5, and 36.6
The novel polymorph Form A of 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]- methyl}1 -methyl-1H-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate) pattern having peaks expressed at 29 at about 4.9, 8.8, 9,2, 9.7, 10.4, 11.6, 12.7, 13.3, 13.8, 14.7, 15.5, 16.5, 16.7, 18.0, 18.9, 20.1, 20.8, 21.6, 22.3, 22.7, 23.3, 23.8, 24.2, 24.7, 26.8, 27.4, 28.2, 28.7, 29.5, 31.3, 32.2, 97.0, 33.8, 34.7, and 36.6
The XRD of novel polymorph Form A of 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]- methyl}-1-methyl-lH-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate) characterized is depicted in Fig. 1.
In another embodiment, the present invention present invention relates to novel polymorph Form A of 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]-methyl}-l-methyl-lH-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate), characterised by melting points of T mp =133±5°C. (form A), (determined by DSC; evaluation by peak maximum; heating rate: 10°C./min) characterized is depicted in Fig. 2.
In another embodiment, the present invention relates to novel polymorph Form A of 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]- methyl}-1-methyl-lH-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate), characterised by TGA characterized is depicted in Fig.
3.
In another embodiment, the present invention present invention relates to novel polymorph Form A of 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]-methyl}-1-methyl-lH-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid

ethyl ester compound of formula I (dabigatran etexilate), characterised by XRD, DSC, TGA which is depicted in Fig. 1 to 3.
The invention also relates to the methods of selectively producing the polymorphic form as well as the modifications which may be obtained by these methods.
In another embodiment, the present invention relates to process for preparation of the form A of 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]- methyl}-l-methyl-lH-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate) is obtained by
a) dissolving 3-[(2-{ [4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]-methyl} -1 -methyl-1 H-benzimidazole-5 -carbony l)-pyridin-2-yl-amino] -propionic acid ethyl ester compound of formula I (dabigatran etexilate) in solvent selected form the group are ethanol, methanol, Isopropyl alcohol, ethyl acetate solvent or acetonitrile and mixtures there off,
b) cooling the solution to precipitate the product
c) washing them with ethyl acetate and
d) isolating the product.
In another embodiment, the present invention provides a process for the preparation of form A of 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]- methyl}-!-methyMH-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate) which comprising step of
a) dissolving 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]-methyl}-l-methyl-lH-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate) in solvent selected form the group are ethanol, methanol, Isopropyl alcohol , ethyl acetate solvent or acetonitrile and mixtures there off;
b) isolating of 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]-methyl} -1 -methyl-1 H-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate).

In another embodiment, the present invention provides a process for the preparation of form A of 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]- methyl}-1-methyl-lH-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate) which comprising step of:
a) treating l-methyl-2-[N-(4-amidinophenyl)-aminomethyl] benzimidazol -5-yl-carboxylicacid -N- (2-pyridyl) -N- (2-ethoxy carbonyl ethyl) -amide compound of formula II or its salt thereof with hexylchloroformate in solvent to obtain compound of formula I;
b) treating 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]-methyl} -1 -methyl-1 H-benzimidazole-5 -carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I with isopropyl alcohol , acetonitrile or ethyl acetate or mixture of solvent; and
c) isolating of 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]-methyl} -1 -methyl-1 H-benzimidazole-5 -carbonyl)-pyridin-2-yl-amino] -propionic acid ethyl ester compound of formula I (dabigatran etexilate).
The crystalline Form A of 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]- methyl}-l-methyl-lH-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate) according to the invention were investigated in more detail by x-ray powder diffraction DSC and TGA. The diagrams obtained are shown in FIGS. 1 to 3.
The present invention is described by the following examples, which are for illustrative purpose only and should not be construed so as to limit the scope of the invention in any manner.
EXAMPLE 1
Preparation of crystalline form A of Dabigatran etexilate:

l-methyl-2-[N-(4-amidinophenyl)-aminomethyl] benzimidazol -5-yl-carboxylicacid -N-(2-pyridyl) -N- (2-ethoxy carbonyl ethyl) -amide hydrochloride was dissolved in acetonitrile and water. Hexyl chloroformate and triethylamine was added to it at a temperature of about 15° C. After the end of the reaction, the precipitated product is filtered off and washed with acetone/water. Dissolved the obtained solid in ethyl acetate under heating and then filtered. The title product was crystallized by the addition of water. The isolated substance is dried under reduced pressure at 45° C.
EXAMPLE 2
Preparation of crystalline form A of Dabigatran erexilate:
l-methyl-2-[N-(4-amidinophenyl)-aminomethyl] benzimidazol -5-yl-carboxylicacid -N-(2-pyridyl) -N- (2-ethoxy carbonyl ethyl) -amide hydrochloride was dissolved in acetonitrile and water. Hexyl chloroformate and triethylamine was added to it at a temperature of about 15° C. After the end of the reaction, the precipitated product is filtered off and washed with acetone/water. Wet cake was dissolved in acetonitrile under heating and then filtered. The reaction mixture was cooled at 25-30°C. The solid product was filtered and dried.
EXAMPLE 2
Preparation of dabigatran etexilate mesylate:
l-methyl-2-[N-[4-(N-n-hexyloxycarbonylamidino)phenyl] amino methyl]benzimidazol-5-yl-carboxylicacid-N-(2-pyridyl)-N-(2-ethoxycarbonylethyl) amide was dissolved acetone under heating. A solution of methane sulfonic acid in acetone was added to the reaction mixture. The solution is filtered and after the addition of acetone cooled to approximately 20° C. The precipitated product was filtered and washed with acetone then dried at 50° C under reduced pressure.

We Claim,
1. A crystalline form of 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]- methyl}-1 -methyl-1 H-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester (dabigatran etexilate) form A.
2. A crystalline form A of claiml is characterised by XRD 20 at about 4.9, 8.8, 9.2, 9.7,10.4, 12.7,13.3, 13.8, 14.7,15.5,18.0,18.9, 20.1, 20.8, 21.6,22.3, 22.7,23.3, 23.8, 24.2, 24.7, 26.8, 27.4, 28.2,28.7,29.5, and 36.6
3. A crystalline form A of claim2 is characterised by XRD figure 1
4. A crystalline form A of claiml is characterised by characterised by melting points of T mp, =133±5°C (determined by DSC; evaluation by peak maximum; heating rate: 10°C./min).
5. A crystalline form A of claim 4 is characterised by DSC figure 2.
6. A crystalline form A of claiml is characterised by TGA figure 3.
7. A process for preparation of the form A of 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylarnino]- methyl}-1 -methyl-1 H-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate) comprises:

a) dissolving 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]- methyl}-1 -methyl-1H-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate) in solvent selected form the group are ethanol, methanol, Isopropyl alcohol , ethyl acetate solvent or acetonitrile and mixtures there off,
b) cooling the solution to precipitate the product

c) washing them with ethyl acetate and
d) isolating the product.
8. A process for the preparation of form A of 3-[(2-{[4-(hexyloxycarbonylamino-
imino-methyl)-phenylamino]- methyl}-l-methyl-lH-benzimidazole-5-carbonyl)-
pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran
etexilate) which comprising step of:
a) dissolving 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]- methyl}-1 -methyl-1 H-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate) in solvent selected form the group are ethanol, methanol, Isopropyl alcohol, ethyl acetate or acetonitrile and mixtures there off;
b) isolating of 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]- methyl}-l-methyl-lH-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate).
9. A process for the preparation of form A of 3-[(2-{[4-(hexyloxycarbonylamino-
imino-methyl)-phenylamino]- methyl}-1 -methyl-1 H-benzimidazole-5-carbonyl)-
pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran
etexilate) which comprising step of:
a) treating l-methyl-2-[N-(4-amidinophenyl)-aminomethyl] benzimidazol -5-yl-carboxylicacid -N- (2-pyridyl) -N- (2-ethoxy carbonyl ethyl) -amide compound of formula II or its salt thereof with hexylchloroformate in solvent to obtain compound of formula I;
b) treating 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenylamino]-methyl}-l-methyl-lH-benzimidazole-5-carbonyl)-pyridin-2-yl-amino]-propionic acid ethyl ester compound of formula I with isopropyl alcohol, acetonitrile or ethyl acetate or mixture of solvent; and
c) isolating of 3-[(2-{[4-(hexyloxycarbonylamino-imino-methyl)-phenyl amino]- methyl}-1-methyl-1 H-benzimidazole-5-carbonyl)-pyridin-

2-yl-amino]-propionic acid ethyl ester compound of formula I (dabigatran etexilate).
10. A process for the preparation of form A according to claim 9 wherein solvent is acetonitrile.