Functional Groups that can use in HSPiP

HSP Application note #24

2010.3.21

HSPiP Team Senior Developer, Dr. Hiroshi Yamamoto

HSPiP(Hansen Solubility Parameters in Practice)

The first edition of HSPiP that appeared in November, 2008, greatly enhanced the usefulness of the Hansen solubility parameters (HSP).

The HSP values of over 1200++ chemicals and 500 polymers are provided in convenient electronic format and have been revised and updated using the latest data sources in the second edition (March, 2009).

A third edition of the HSPiP appeared in March, 2010. There are now 10,000 compounds in the HSP file which also includes data on density, melting point, boiling point, critical parameters, Antoine constants and much more. The user is able to carry out many different sorts of optimisations of solubility, evaporation, diffusion, adhesion, create their own datasets (automatically if required) and explore the huge range of applications for HSP in coatings, paints, nanoparticles, cosmetics, pharma, organic photovoltaics and much more.

The 3rd Edition v3.1 was released on 12 December 2010.
The 4th Edition v4.0.x was released on 2 Jan. 2013.
The v4.1.x was released on 18th Aug. 2013

The Current users can upgrade with free charge.

2013.1.28 The Visual How to manual of HSPiP. You can understand what HSPiP can do.

How to purchase HSPiP
2013..1.2 The HSPiP ver. 4 include Power Tools for HSPiP power user.

Functional Group s (FG) used in version 3 (to ver. 4.1.x). Y-Predict use same FG.
Please check your compound whether all of functional groups are in the list.

Y-MB break molecule as to below list.
Y-MB choose larger FG if it available.
Y-MB can not handle charged atoms like N+, Cl-.

@ mark means Attach to.
# means triple bond.
The FG used in the cyclic part, _R is added.

Alkane groups

1	CH3	16	Bu	23	CH2CH2
2	CH2	17	2_Bu	24	CH2CH2_R
3	CH	18	iso_Bu	25	CH2CH2CH2
4	C	19	ter_Bu	110	CH2CH2CH2_R
11	CH2_R	20	Pr	128	CH2CH2CH2CH2
12	CH_R	21	iso_Pr	129	CH2CH2CH2CH2_R
13	C_R	22	Et	26	CH3_C_CH3

Olefine groups

5	CH2:	9	#CH
6	CH:	10	#C
7	C:	14	CH:_R
8	:C:	15	C:_R

Hydroxy groups

27	OH	117	OH@Ph
28	2_OH	121	OH@N
29	3_OH	147	OH_Other

Ketone groups

32	C:O	166	C:O_R@AR
33	C:O_R	120	C:O@Hal
165	C:O@AR	136	C:O@N

Ester groups

36	COO	161	COO@AR
37	COO_R	162	COO_R@AR
101	HCOO

Carboxylic acid groups

COOH

COOH@AR

Aldehyde groups

HCO

100

CHO@Ar

Nitrile groups

C#N

C#N@AR

Nitrile group is very difficult group. The properties are very depend on attached groups. We recommend only alkane or Aromatic attached nitrile.

Acid anhydride groups, Carbonate groups

57	OCOO	59	COOCO
58	OCOO_R	60	COOCO_R

Ether groups and other oxygen

30	O	130	O@P	106	O_reso
31	O_R	131	O@S	112	O-ethylene
102	O_R@AR	132	O@Si	151	O@Other
167	O@AR	104	OO	156	O_EPO
122	O@N			135	O:

Ether attached to halogen groups, especially CF2,
that loss ether properties.

Sulfer groups

46	SH	103	S@AR
47	S	105	S_R@AR
48	S_R	160	SH@AR
49	SS

Other Sulfer groups

52	S:O	107	COS
119	S:	108	S_reso
		127	S{:O}2

SO2 group attach to NH2 or NH, the properties are similar to Amide.
But in ver. 3 we use just SO2+NH2.

Amine groups

38	NH2	87	NH2@Ar
39	NH	163	NH@AR
40	NH_R	164	NH_R@AR
41	N	139	N@AR
42	N_R	140	N_R@AR

Other nitrogen groups

153	N:C	144	N:_reso	50	N3res
154	N:C_R	157	N:CH	51	NHres
155	N:N	158	N:CH_R	43	N:
				148	N#C

Nitro groups

NO2

NO2@AR

134

NO3

Amide urethane groups

53	NHCO	55	NCO	99	NHCOO
54	NHCO_R	56	NCO_R	152	C:ONHC:O

Aromatic groups

63	Ph	123	3s_Ph	141	1s_Naph	159	C:_rrr
65	o_Ph	124	4s_Ph	142	2s_Naph	145	CH:_reso
66	m_Ph	125	5s_Ph	143	3s_Naph	146	C:_reso
67	p_Ph	126	6s_Ph

C:_reso means resonance carbon connect to alkane carbon.
CH:_reso means resonance carbon connect to hydrogen.
C:_rrr means resonance carbon like the naphthalene center 2 carbon.
Xs_Ph: means X substitute.

Hydrogen & Halogen Atom

88	H
89	F	93	F@Ar	109	F_Ole
90	Cl	94	Cl@Ar	118	Cl_Ole
91	Br	95	Br@Ar
92	I	96	I@Ar

Halogen groups

70	CF3	74	CF2_R	81	CF
71	CCl3	75	CF2	84	CCl
72	CF2Cl	77	CCl2	114	CF_R
73	CFCl2	79	CFCl
76	CHF2	82	CHF	68	C2F5
78	CHCl2	85	CHCl	69	C2F4H
80	CHFCl	111	CHCl_R
83	CH2F	113	CHF_R
86	CH2Cl	115	CFCl_R
		116	CCl2_R

Other hydrogen atom

H@N

H@C=O

138

H@Si

Other atom

137	Si	149	P	150	B
		133	P:O

P is parameter missing for HSP

If I increase Functional Groups, properties estimation accuracy will increase.
But Functional Groups number increase, I need more and more data.

If you want to ask me to add new FG, please send me, at least, density, vapor pressure data, heat of vaporization, Refractive Index, Dipolemoment, dielectric constant for that molecule.

For Y-predict user. 2013.9.7

The Functional Group list is same with Y-MB.
There is one discussion about 3s_Ph or pyridazine compounds. For 3s_Ph, there are 1-2-3, 1-2-4, 1-2-5, 1-3-5 substitutions. But Y-MB and Y-Predict treat just same 3s_Ph. Some case, substitution position may change some properties, but to increase FG I need so many data but hard to get them.

For Y-Predict, I put the QEQ charge calculation function.

For these 3 compounds, FG list are same (N=_reso 2 , CH=_reso 4). But as you see, Nitrogen atom's charge are different (-0.045, -0.105, -0.064). So it means tree types of N=_reso exist. And in the calculation result, there is term of Symmetry Index. First and third molecule has 100% Symmetry, but second molecule is not 100% Symmetry. This Symmetry is "charged base" symmetry.The Max Plus Charge, Minimum Minus Charge are also different to these 3 molecules.

Application of these chrages and Symmetry to properties estimations scheme is just starting. If I find rational way to use of these Indexes, I will put them in new version.

Hansen Solubility Parameters(HSP) Application Notes